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EP1824929B1 - Composition de polypropylene presentant une resistance a la rayure amelioree - Google Patents

Composition de polypropylene presentant une resistance a la rayure amelioree Download PDF

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Publication number
EP1824929B1
EP1824929B1 EP05814250A EP05814250A EP1824929B1 EP 1824929 B1 EP1824929 B1 EP 1824929B1 EP 05814250 A EP05814250 A EP 05814250A EP 05814250 A EP05814250 A EP 05814250A EP 1824929 B1 EP1824929 B1 EP 1824929B1
Authority
EP
European Patent Office
Prior art keywords
polypropylene
composition
composition according
olefin
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP05814250A
Other languages
German (de)
English (en)
Other versions
EP1824929A1 (fr
Inventor
Peter Neuteboom
Maria Soliman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saudi Basic Industries Corp
Original Assignee
Saudi Basic Industries Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saudi Basic Industries Corp filed Critical Saudi Basic Industries Corp
Priority to EP05814250A priority Critical patent/EP1824929B1/fr
Publication of EP1824929A1 publication Critical patent/EP1824929A1/fr
Application granted granted Critical
Publication of EP1824929B1 publication Critical patent/EP1824929B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond

Definitions

  • the present invention is directed to a polypropylene composition having improved scratch resistance properties.
  • polypropylene composition has an excellent combination of properties such as for example impact resistance, elongation at break, modulus and dimensional stability.
  • composition according to the present invention can be injection moulded at a high injection rate while the moulded part thus obtained does not exhibit (or at least exhibits them to a strongly reduced extent) surface defects in the form of a stripe or a pattern.
  • the polypropylene in the composition according to the invention may be a homopolymer as well as a copolymer, particularly all kinds of reactor copolymers, for instance block copolymers (blends of a homopolymer and a rubber, for instance an EPR rubber) may be used.
  • block copolymers blends of a homopolymer and a rubber, for instance an EPR rubber
  • Many types of polypropylene are commercially available and they can be readily prepared by methods well known and extensively described in the art using for instance conventional Ziegler-Natta catalysts as well as single site catalysts, for instance metallocene catalysts. Of course, also mixtures of different types of polypropylene can be used.
  • the MFI of the polypropylene may range between wide limits, for instance between a lower limit of 0.1 g/10min and an upper limit of 100 g/10min.
  • the lower limit is 10 g/10min and more preferably the lower limit is 20 g/10min.
  • the polypropylene homopolymer has an isotactic structure, which means that the isotacticity is high, for instance higher than 95% and preferably higher than 98%.
  • the propylene is a copolymer of propylene and of an olefin other than polypropylene.
  • the olefin other than propylene may be for instance an ⁇ -olefin, in particular 1-alkene having for instance 2 or 4-20 C-atoms or cyclic olefins, optionally containing more than one ring, having a double bond in the ring structure.
  • suitable olefins include ethylene, butene, hexene, styrene, cyclopentene and/or norbornadiene.
  • the ⁇ -olefin is a 1-alkene having 2 or 4-8 C-atoms.
  • the ⁇ -olefin is ethylene.
  • the composition comprises 60- 80wt% polypropylene.
  • the polypropylene may contain rubber.
  • the polypropylene composition may comprise in an amount of, for instance, 0-30 wt.% of a rubber, preferably 5-20 wt.%, with a comonomer content of, for instance 10 -70 wt.%, preferably 30 -65 wt.%.
  • the rubber is an ethylene propylene rubber (EPR rubber).
  • EPR rubber ethylene propylene rubber
  • the EPR rubber has an ethylene content of, for instance 20 -70% and more preferably of 50 -65 wt.%.
  • the polypropylene may also contain a modified polypropylene.
  • suitable modified polypropylenes are polypropylenes grafted with for instance an unsaturated organic compound, for instance a carboxylic acid, an anhydride, an ester, or salts thereof or maleic, fumaric, (meth)acrylic, itaconic or cinnamic acid or anhydride, ester or salt thereof.
  • maleic anhydride is used.
  • the amount of modified polypropylene may vary within wide limits. For economical reasons the amount normally will be rather low, for instance lower than 10 wt.%, preferably 0-3 wt.% modified polypropylene calculated with respect to the total amount of polypropylene.
  • composition according to the invention contains 2-20 wt.% long-chain branched low density polyethylene (LDPE).
  • LDPE long-chain branched low density polyethylene
  • the composition contains 5-15 wt.% long- chain branched low density polyethylene.
  • Long-chain branching describes the configuration of the polymer molecule possessing side chains with a degree of polymerization of the same order as that of the main chain.
  • the density of the polyethylene ranges between 910 kg/m 3 and 935 kg/m 3 and the melt index ranges between 0.10 dg/minute and 100 dg/minute preferably between 8 to 80 g/10min (the MFI is measured in accordance with ISO 1133 using a 2.16 kg weight and at a temperature of 190°C).
  • the density of the polyethylene ranges between 915 kg/m 3 and 935 kg/m 3
  • the melt index of the polyethylene ranges between 50 and 70 g/10min.
  • composition according to the invention comprises 1-20 wt.% of a copolymer of ethylene and a C 3 -C 20 ⁇ -olefin.
  • the copolymer of ethylene and a C 3 -C 20 ⁇ -olefin has a density between 840 and 890 kg/m 3 .
  • the MFI of the copolymer of ethylene and a C 3 -C 20 ⁇ -olefin is between 0.1 and 100 g/10min (measured in accordance with ISO 1133 using a 2.16 kg weight and at a temperature of 190 °C).
  • the density of the copolymer of ethylene and a C 3 -C 20 ⁇ -olefin is between 860 and 880 kg/m 3 .
  • the MFI of the copolymer of ethylene and a C 3 -C 20 ⁇ -olefin is between 0.1 and 10 g/10min.
  • composition according to the invention may comprise a mixture of copolymers of ethylene and a C 3 -C 20 ⁇ -olefin.
  • the polypropylene composition according to the invention comprises 1-18 wt.% of the copolymer of ethylene and a C 3 -C 20 ⁇ -olefin.
  • the polypropylene composition comprises 5-15 wt.% of the copolymer of ethylene and a C 3 -C 20 ⁇ -olefin.
  • Suitable fillers include for example talc, glass beads, glass fibers, clay, mica, wollastonite, calcium carbonate, silica, carbon black and/or titanium oxide. According to a preferred embodiment of the invention the filler is talc, glass fiber or carbon black.
  • the amount of filler in the polypropylene composition according to the invention is between 0,5 and 60 wt.%. Fillers amounts above 40 wt.% will normally be present in mixtures of a homopolymer of polypropylene and filler or in concentrates (i.e. compositions that normally will be mixed with other compositions before being further processed, for instance moulded).
  • compositions used for further processing into articles preferably contain for instance more than 1 wt.% filler, particularly more than 2 wt.% filler, most preferably more than 5 wt.% filler and less than 45 wt.% filler, particularly less than 30 wt.% filler, most preferably less than 20 wt.% filler.
  • the composition according to the invention comprises in addition to said components a slip agent.
  • the amount of slip agent to be used may range between wide limits, for instance between 0 and 3 wt.%.
  • the amount of slip agent ranges between 0.1 and 1 wt.%, calculated with respect to the polypropylene composition.
  • Suitable slip agents include for example fatty acid amides and/or polysiloxanes.
  • Suitable fatty acid amides are for instance saturated and unsaturated amides or saturated and unsaturated alkylenebisamides.
  • suitable amides include palmitamide, stearyl araffleamide, stearamideoethylstearamide, stearamidoethylpalmitamide, erucamide, oleamide, erucamidoethylerucamide, stearamidoethylerucamide and/or oleoamidoethylerucamide.
  • the slip agent is a fatty acid amide.
  • composition according to the invention may optionally contain additives, for instance nucleating agents and clarifiers, stabilizers, release agents, fillers, plasticizers, anti-oxidants, colorants, ignition resistant additives, lubricants, mold releases, flow enhancers and/or antistatics.
  • additives for instance nucleating agents and clarifiers, stabilizers, release agents, fillers, plasticizers, anti-oxidants, colorants, ignition resistant additives, lubricants, mold releases, flow enhancers and/or antistatics.
  • additives are well known in the art and the skilled person will select the type and amount of additives such that they do not detrimentally influence the aimed properties of the composition.
  • the amount of additives may vary between wide limits, for instance from 0 up to 20 wt.%, particularly between 1 and 10 wt.%, calculated with respect to the polypropylene composition.
  • the propylene copolymer composition according to the invention is suitable to be used for instance in blow molding, injection molding or extrusion of moldings, films, sheets or pipes to be applied in a wide range of articles such as for instance, exterior and interior automotive parts, especially esthetic (non painted visible) parts, such as for example bumper beams, bumper fascia, instrument panels and pillars, thin wall packaging, caps and closures, pails and containers, crates and boxes, cans and bottles, appliance housings, houseware, toys, multi-media packaging, electrical applications, for example electrical equipment housing, lawn and garden furniture and construction sheet.
  • esthetic (non painted visible) parts such as for example bumper beams, bumper fascia, instrument panels and pillars, thin wall packaging, caps and closures, pails and containers, crates and boxes, cans and bottles, appliance housings, houseware, toys, multi-media packaging, electrical applications, for example electrical equipment housing, lawn and garden furniture and construction sheet.
  • the propylene copolymer composition according to the invention is very suitable to be applied in visible interior automotive parts such as for example instrument panels and pillars.
  • compositions according to the invention may be performed according to any suitable mixing procedure.
  • suitable mixing procedure such as for example dry blending the individual components, optionally followed by melt mixing, and subsequently extrusion or directly injection moulding.
  • a composition was obtained by compounding the ingredients according to Table 1 at 210 °C in a co-rotating twin-screw extruder. The composition was then injection moulded into plates of 65 x 65 x 3.2 mm according to ISO 37-2. The appropriate samples were machined out of the plates.
  • test results are given in Table 1.
  • the amounts used are given in wt.% calculated with respect of the total composition.
  • Example I was repeated except that LDPE was replaced by HDPE.
  • Table 1 Composition Example I Comparative Example A Polypropylene 1 wt.% 59.3 59.3 LDPE 2 wt.% 8 - HDPE 3 wt.% - 8 Copolymer 4 wt.% 10 10 Filler 5 wt.% 20 20 Slip Agent 6 wt.% 0.6 0.6 Additives 7 wt.% 2.1 2.1 MFI (ISO 1133) dg/min 27 25 Izod Impact (notched) @ 0 °C (ISO 180 4A) kJ/m 2 6 7 Izod Impact (notched) @ 23 °C (ISO 180 4A) kJ/m 2 34 24 E-modulus ASTM D790) N/mm 2 1600 1700 Shrink (ISO 294 3&4)
  • the scratch resistance was measured according to the VW PV 3952 scratch method with a load of 10N using VW texture K59. (VW means Volkswagen)
  • the colour of the scratch was measured relative to the unscratched surface.
  • the colour was measured according to ISO 7724 (1984).
  • the resulting value dL is a measure for the scratch resistance because a low dL value corresponds to a high scratch resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (12)

  1. Composition de polypropylène comprenant :
    (i) de 30 à 97% en poids d'un polypropylène ;
    (ii) de 2 à 20% en poids d'un polyéthylène à faible densité ramifié, présentant une densité comprise entre 910 et 935 kg/m3 et un indice de fluidité à chaud (IFC) compris entre 0,1 et 100 g/10 min ;
    (iii) de 1 à 20% en poids d'un copolymère de l'éthylène et d'une α-oléfine en C3-C20 présentant une densité comprise entre 840 et 890 kg/m3 et un indice de fluidité à chaud (IFC) compris entre 0,1 et 100 g/10 min ; et
    (iv) de 0,5 à 60% en poids d'une charge,
    où les pourcentages en poids sont calculés par rapport à la quantité totale de la composition de polypropylène.
  2. Composition selon la revendication 1, dans laquelle la quantité du polyéthylène à faible densité ramifié est comprise entre 5 et 15% en poids.
  3. Composition selon l'une quelconque des revendications 1 à 2, dans laquelle la densité du polyéthylène à faible densité ramifié est comprise entre 915 et 925 kg/m3.
  4. Composition selon l'une quelconque des revendications 1 à 3, dans laquelle le polyéthylène à faible densité ramifié présente un indice de fluidité à chaud compris entre 8 et 80 g/10 min.
  5. Composition selon l'une quelconque des revendications 1 à 4, dans laquelle la quantité du copolymère de l'éthylène et d'une α-oléfine en C3-C20 est comprise entre 1 et 18% en poids.
  6. Composition selon l'une quelconque des revendications 1 à 5, dans laquelle le copolymère de l'éthylène et d'une α-oléfine en C3-C20 présente une densité comprise entre 860 et 880 kg/m3.
  7. Composition selon l'une quelconque des revendications 1 à 6, dans laquelle l'IFC du copolymère de l'éthylène et d'une α-oléfine en C3-C20 est compris entre 0,1 et 10 g/10 min.
  8. Composition selon l'une quelconque des revendications 1 à 7, où la composition comprend entre 60 et 80% en poids d'un polypropylène.
  9. Composition selon l'une quelconque des revendications 1 à 8, où la composition comprend en outre un agent de glissement.
  10. Composition selon l'une quelconque des revendications 1 à 9, dans laquelle la quantité de charge est de 1 à 45% en poids.
  11. Article composé d'une composition selon l'une quelconque des revendications 1 à 10.
  12. Pièce intérieure d'automobile composé d'une composition selon l'une quelconque des revendications 1 à 10.
EP05814250A 2004-12-16 2005-11-30 Composition de polypropylene presentant une resistance a la rayure amelioree Not-in-force EP1824929B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05814250A EP1824929B1 (fr) 2004-12-16 2005-11-30 Composition de polypropylene presentant une resistance a la rayure amelioree

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP04078423 2004-12-16
EP05814250A EP1824929B1 (fr) 2004-12-16 2005-11-30 Composition de polypropylene presentant une resistance a la rayure amelioree
PCT/EP2005/012947 WO2006063698A1 (fr) 2004-12-16 2005-11-30 Composition de polypropylene presentant une resistance a la rayure amelioree

Publications (2)

Publication Number Publication Date
EP1824929A1 EP1824929A1 (fr) 2007-08-29
EP1824929B1 true EP1824929B1 (fr) 2009-03-25

Family

ID=34928748

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05814250A Not-in-force EP1824929B1 (fr) 2004-12-16 2005-11-30 Composition de polypropylene presentant une resistance a la rayure amelioree

Country Status (9)

Country Link
US (1) US7888423B2 (fr)
EP (1) EP1824929B1 (fr)
JP (1) JP4842277B2 (fr)
KR (1) KR101224331B1 (fr)
CN (1) CN101080460B (fr)
AT (1) ATE426637T1 (fr)
DE (1) DE602005013569D1 (fr)
ES (1) ES2322281T3 (fr)
WO (1) WO2006063698A1 (fr)

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ES2626661T3 (es) 2011-07-27 2017-07-25 Borealis Ag Resina de polipropileno ligero con características superficiales superiores para uso en aplicaciones interiores de automóviles
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KR101638710B1 (ko) 2011-08-11 2016-07-11 보레알리스 아게 개선된 장기간 스크래치 저항성 및 감소된 표면 점착성을 갖는 조성물
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MY173740A (en) * 2014-01-29 2020-02-18 Korea Pallet Pool Co Ltd Composition comprising glass fiber and two or more types of resin
JP6223940B2 (ja) * 2014-09-26 2017-11-01 共栄産業株式会社 樹脂シート及び樹脂
EP3237535B1 (fr) 2014-12-22 2021-01-27 SABIC Global Technologies B.V. Composition de polypropylène
JP6720804B2 (ja) * 2015-10-09 2020-07-08 日本ポリプロ株式会社 熱成形用シートおよび成形体
KR20170143260A (ko) * 2016-06-21 2017-12-29 (주)켐코정밀 자동차 내외장재용 폴리프로필렌 복합수지의 내스크래치성능 개선을 위한 탈크 마스터배치 수지 조성물
KR101883549B1 (ko) * 2016-06-21 2018-07-30 (주)켐코정밀 자동차 내외장재용 폴리프로필렌 복합수지의 내스크래치성능 개선을 위한 탈크 마스터배치 수지 조성물의 제조방법
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CN117430892A (zh) * 2023-11-30 2024-01-23 金发科技股份有限公司 一种聚丙烯组合物及其制备方法和应用

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Also Published As

Publication number Publication date
JP4842277B2 (ja) 2011-12-21
US20090105402A1 (en) 2009-04-23
DE602005013569D1 (de) 2009-05-07
CN101080460B (zh) 2010-05-12
ATE426637T1 (de) 2009-04-15
ES2322281T3 (es) 2009-06-18
CN101080460A (zh) 2007-11-28
US7888423B2 (en) 2011-02-15
JP2008524348A (ja) 2008-07-10
KR20070098844A (ko) 2007-10-05
WO2006063698A1 (fr) 2006-06-22
KR101224331B1 (ko) 2013-01-18
EP1824929A1 (fr) 2007-08-29

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